CA1048043A - Production of phosphorus-containing esters - Google Patents

Production of phosphorus-containing esters

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Publication number
CA1048043A
CA1048043A CA222,997A CA222997A CA1048043A CA 1048043 A CA1048043 A CA 1048043A CA 222997 A CA222997 A CA 222997A CA 1048043 A CA1048043 A CA 1048043A
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Prior art keywords
carbon atoms
phosphorus
stands
reaction zone
alcohol
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Expired
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CA222,997A
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French (fr)
Inventor
Elmar Lohmar
Paul Stutzke
Klaus Gehrmann
Alexander Ohorodnik
Horst Staendeke
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PRODUCTION OF PHOSPHORUS-CONTAINING ESTERS
ABSTRACT OF THE DISCLOSURE:

Production of phosphorus-containing esters of the general formula:

in which X stands for an alkyl group having from 1 to 3 carbon atoms, an aryl group or an alkoxy group having from 1 to 6 carbon atoms, Y stands for an alkoxy group having from 1 to 6 carbon atoms, and Z
stands for a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms, an aryl group or an alkoxy group having from 1 to 6 carbon atoms. The esters are produced by reacting one or more phosphorus halides of the general formula:

Description

~41~Q43 In making esters of phosphoric acid, phosp~orous acid, alkane or arylphosphonous acids, alkane or aryl-- phosphinic acids and alkyl or arylphosphonic acids, it is good practice to use the corresponding acid halides, e.g. the chlorides, as starting material.
- It ~s known that those esters can be made ~ro~
phosphoric acid halides by reactir,~ them with alcohols.
For example, it is possible to produce phosphorous acid dialkylesters by reacting PCl3 with e~uimolar praportions of an alcohol in accordance with the ~ollowing equation (1):

(1) PCl3 ~ 3 ROH ~ -> (RO)2P + RCl ~ 2 HCl-- \ H

(Houben-W~ l, "Methoden der Organischen Chemie", , ~
volume i~t~-, (1964~, Pages 21-28).
Symmetrical phosphoric acid triesters can be produced as shown by the following equation (2)
(2) POC13 + 3 ROH ----- > (RO) PO + 3 HCl .
~H~ ben-Weyl, "Methoden der Organischen Chemie", volume (1964), pages 310-315).
arc~Phos~o c~r Monoesters of alkane or ~ acids can also be made by reacting the corresponding alkyl or aryl-chlorophosphines with alcohols in accordance with eQu~tion (3) ~ ~~
', .

.' ._, ..... ' . ~ ~ .

~)4~{~43 11 .
(3) R-PCl2 ~ 2 R'OH~R-IP-H -~ HCl + R'Cl OR' (Houben-Weyl7 "Methoden der Organischen Chemie", volume ~2/1 (1963), pages 320-323), Diesters of alkane or arylphosphonic acids can be made as shown by equation (4):
(4) R-POCl2 + 2 HO-R' -~R-P(OR')2 + 2 HCl (Houben-Weyl, "Methoden der Organischen Chemie", volume 12/1, (1963), pages 423-430).
Es-ters of dialkyl, diaryl or arylalkylphosphinic acids are obtainable by reacting the corresponding acid chlorides with alcohols in accordance with equation (5):
.
(5) RzP(O)Cl + R~ok~ R2P(O)OR' + HCl . . :
(Houben-Weyl, i'Methoden der Organischen Chemie", volume 12/1, (1963), pàges 248-249).
As descrlbed in the art, it is customary for phosphorus-containing esters to be produced at low temperatures, commonly in the presence of bases sequesterirlg the resulting hydrogen chloride~. This is more-particularly true concerning reactions, wherein PC13 and R-PCl2 are used as the starting materials. me bases used therein include amnmonia and organic nitrogen bases, such as amines or pyridines. The use OI inert solvents is also typical of the processes described .
'~ .

~L~4~3 heretofore. During manufacture, it is necessary for base hydrochloride to be filtered off and for the inert solvent to be separated. After this has been done, the phosphorus-containing ester can be obtained, commonly by distillative treatment. The prior processes for making phosphorus-containing esters are rendered costly and difficult by the facts that they are carried out at low temperatures within the range -30 and +20C with the use of inert solvents and bases sequestering the hydrogen chloride, and that it is necessary for the base hydrochloride to be filtered off from the reaction mixture.
The present invention now provides a process for making phosphorus-containing esters of the general formula:
o X-P-Z, y in which X stands for an alkyl group having from 1 to 3 carbon atoms, an aryl group or an alkoxy group having from 1 to 6 carbon atoms, Y stands for an alkoxy group having from 1 to 6 carbon atoms, and Z stands for a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms or an aryl group, by reacting one or more phosphorus halides of the general formula:

A-P-C, D

in which A and B stand independently from one another for a chlorine or bromine atom, an alkyl group having from 1 to 3 carbon atoms or an aryl group, C stands for a chlorine or bromine atom and D stands for a free pair of electrons or an oxygen atom, with aliphatic alcohols having from l to 6 carbon atoms, which process comprises heating to boiling, in a reaction zone, the phosphorus halide and the aliphatic alcohol at temperatures within the range 60 and 150C, passing the resulting hydrogen halide and alchol in excess to the upper portion of the reaction zone, condensing it therein and removing it therefrom; and flowing resulting phosphorus-containing ester, if desired with an excess of aliphatic alcohol, to the lower portion of the reaction zone and removing it therefrom.
The phosphorus halide compounds which may be used in the present process include, for example: phos-phorus trichloride, ~ethyldichlorophosphineg ethyldichloro-phosphine, propyldichlorophosphine, phenyldichlorophos-phine, phosphorus oxychloride, methanephosphonic acid dichloride, ethanephosphonic acid dichloride, propanphos-phonic acid dichloride, phenylphosphonic acid dichloride, dimethylphosphinic acid chloride, dipropylphosphinic acid chloride, methylethylphosphinic acid chloride, methyl-propylphosphinic acid chloride, ethylpropylphosphinic acid chloride and the corresponding bromides.
Useful alcohols are, for example, methanol, ethanol, n-propanol, i-propanol, n-butanol and similar alcohols, isobutanol being particularly preferred.
It is very advantageous to effec~ the reaction 8~
in the presence of nitrogen, argon or carbon dioxide as an inert gas. The reaction zone should pre~erably be supplied continuously, per mol of phosphorus halide, ~with 1.2 -to ~ times -the s-toechiome-tric quantity of alcohol, the quantity of alcohol~ which is introduced once into the reac-tion zone to initiate the reaction, being ignored. The alcohols should preferably contain less than 0.5 weigh-t /0, more preferably less than 0.1 weight %, o~ water.
It is preferable for the reaction to be effected at temperatures close to the boiling point to the mixture of alcohol and resulting phosphorus-containing es-ter, i.e. at temperatures wi-thin the range 78 and 110C, if ethanol is used, or a-t temperatures within the range 108 and i40C, if lSO-bu-tanol is used.
It is even more preferable for the reac-tion to be e~fected in the following manner: phosphorus halide and aliphatic alcohol in liquid or vapor form are supplied continuously, in the molar ratio indicated hereinabove, to a reaction zone, e.g. a column, heated to boiling therein, whereby the resulting hydroge~ halide and a portion of the boiling alcohol are delivered to the upper portion of the zone, in which they are distilled, continuously condensed and removed therefrom9 whereas the resulting phosphorus-containing ester, which is the higher boiling ingredient of the mixture, is delivered3 if desired together with a portion of boiling a1~ohol, to the lower portion of the zone and ;
continuously removed therefrom.

- ` - 6 1~481V43: . :
The react.ion products are worked up inknown manner, It is possible for the phosphorus-containing ester to be freed distilla-tlvely from aliphatlc alcohol in excess, if 'desired a~ter neu-tralization of the solution.The distillate ' consisting of hydrogen halide, aliphatic alcohol and alkyl halide, if any, which lS removed from the upper~portion 'of ~
the reaction zone, is also separated by conventional ' ' ' - methods and the alcohol is rècovered there~rom.
~, ' The process of the present inven-tion unexpectedly enables the dçcomposition of the resultlng phosphorus- '~
'containing ester by hydrogen halide, which is formed thereinj to be substantially lnhibited. This is due to ' the fact that the reaction heat which is set free upon , the reaction of the phosphorus halide wlth the aliphatic alcohol~ makes it impossible for the hydrogen halide to . .
remain in contact for some prolonged time with the ~ resulting phosphorus-containing ester. The hydrogen - ~ hallde rather escapes at once lnto the upper portion of the reaction zone and is thus separated from the ~ -phosphorus-containing ester which in turn, as the ' ; higher-boillng component, is delivered to the lower~
.- ' portion o~ the reaction 20ne.
' m e process of the present inventlon compares~
' favorably with the prior art in various respècts~
- The phosphorus-containing'ester is separated ver~
rapidly and in a manner which is typical of the present process ~rom hydrogen halide which'is formed slmultaneously ~~erewith. In other words, the~hydrogen .' halide is considerably less likely to catalyze th~e~ 'S`!^`';
: 30 decomposltion o~ the phosphorus-containing ester~

which is accordingiy obtained in improved yields. In the prior art processes, it is necessary to use bases, such as ammonia or organic amines, ~or sequestering all the hydrogen halide in the form of ammonium or amine hydrohalide salts, which precipitate and are filtered off with heavy loss o~ material. A portion o~
the base hydrohalides remains, however, dissolved and ef~ects the catalytic decomposition of the phosphorus-containing es-ters, whereby the yield is impaired~ These are disadvantageous effects which are not encountered in the process o~ the present invention. The phosphorus-containing esters are obtained in more concentrated form than in all prior art processes. The heat, which is set ~ree on reacting the phosphorus halides with aliphatic alcohols -- this being an exothermal reaction -- at the boiling poin-t of the mix-ture, is dissipated by~"vapor cooling" and the hydrogen halide is removed jointly therewith. In prior art processes, wherein the reactio~
is effected stagewise, such heat is required to be dissipated through the reactor wall so as to permit hydrogen halide~ which is retained in the solution, to be neutralized in an equally highly exo-thermal reaction, and thereafter to be dissipated once again through the reactor wall, this time in a liquid medium which becomes increasingly more viscous by solid base hydrohalide, which precipitates therein.
In those prior processes which are carried out, e.g. with the use o~ an ammonia base and a chlorine-containing compound, it is additionally necessary for precipi;ated microcrystalline ammonium chloride to be - 8 ~
'., : '' .. . ~ ~, ~f~14~3~4;~
stirred for some hGurs in the reaction medium to effect recrystallization of the salt and its transfor,mation into fil-terable material. The capaci-ty of the apparatus is substantially a ma-tter of,indifference in the ' commercial process of the present invention which provides for an uninterrupted delivery of starting ' ' ~' material to~ and removal of flnal product from, the reaction zone. Thls is in clear con-trast with the known preparation in stages producing limited space~time-yields, which are criti,cally affected by the ,cooling , ;' area of the reactor, In additlon to this, stagewise ~ -operation is rendered very expenslve by the need to appropriately dimension'-the apparatus for filtering ' ~ ;
the base hydrohalide.
Phosphorus-containing esters having P-H bonds thereln are very,useful starting materials for making ', ~lameproofing agents for polyesters, polyurethanes and polyacrylonitrile. Theseare very pure and accordingly well adapted for use in reac-tions which are catalyzed ' -~
by radical yLelding agents.
'~ . . , ' : ' ' ~'~
EXAMPLE 1~
- ~Methanephosphonous acid isobutylester; cf.
' equation ~3 ', An apparatus such as that shown in the accompanying drawing was usèd. 900 ml (722 g =' ~ mol) of iso~
- , : ~ : .
butanol was so introduced into circulation evaporator ,~
(1) and heated t~ boiling -therein while nitrogen~was supplied a-t a ra~e of 2 - 3 l/h t~at the boiling temperature of 1~8C was reached near the head of ~IL63 9~8~L3 column (2), below cooler (3). At that temperature, 130 g/h (1.~1 mol) of methyldichlorophosphine i~ vapor form was introduced approximately in-to the center portion of column (2), through inlet (10) and preheater (8). 292 g/h (3.95 mols) of iso-butanol, which was partially in vapor form and partially in liquid form, was introduced into column (2) substantially at the same level, through inle-t (11) and preheater (9). The temperature in the~
circulation evaporator (1) increased from 108 to 135C
and was 110C in the column base portion. In the center~ -portion of the column, where the reaction took place, the temperature was between 97 and 112C, and it dropped to 95C during the reac-tion, near the head of the -~
column. A mixture of iso-butanol, iso-bu-tylchloride and hydrogen chloride distilled off near the head of the column, through line (4). Reaction product was~removed continuously from the circulation evapora-tor (1), once the temperature was at 135C therein, through line (7).
Altogether 4.22 mols of methyldichlorophosphine and 15 mols o~ iso-butanol were supplied within 3.8 hours.
The experiment was interrupted, the material in the column base (altogether 959 g) was remo~ed co~pletely and the reactlon product was subjected to gas chromato-graphy. It contained 58.2 weight % (55~ g = 4.1 mols) of methanephosphonous acid monoisobutyl ester ~97.2 %
o~ the theoretical)~ The distillate in recelver~(5) `~;
contained 3.59 mols of hydrogen chloride. A further 0.63 mol of HCl was in an off-gas scrubber ~6~, placed downstream of receiver (5)~ wherein the off-gas was 0 scrubbed with water. The distillate obtained near the `

'~

-head of the column could not be found -to contain methanephosphonous acid monoisobutyl ester or diiso-butylester. The p~osphorus content was 0.03 weight %.

EXAMPLE 2: (Comparative Example) A solution of 58.5 g (0.5 mol) of methyldichloro-phosphine in 300 ml of anhydrous ether was admixed dropwise under nitrogen, with agitation and while coollng, with 88.8 g (1.2 mol) of iso-butanol and 50.5 g 10:~ (0.5 mol) of triethylamine in 100 ml of anhydrous ether.
The whole was reflux-heated for 30 minu-tes at 35C, - then cooled down to 5C and fil-tered. The filtrate was concentrated and vacuum-distilled under nitrogen. Iso-butanol and iso-butyl chloride in excess were remo~ed together with the first runnings. 59.8 g (0.44 mol~ of methanephosphonous acid isobutylester (88 %~of~the theoretical) was obtained as the main produc-t.
. ' --EX~MPLE 3: ~Comparative Example) 20 ~ A rea¢tion flask was fed with 2220 g (30 mols) of iso-butanol which was admixed dropwise within Z hours ;
under nitrogen, with agitation and while cooling down to less than 20C, with 585 g ~5 mols) of methyl-dichlorcphosphine-.
The whole was neutralized for 3 hours wlth gaseous~
- ammonia with agitation and while cooling down to less - than 30~:C. Agitation was continued for about a further 8 hours to effect recrystallization of the ammonium chlor:ide which was suction~filtèred. The filter cake was washed twice~ each time with 200 g of iso-butanol.

~04~3 The filtrate (3220 g) was subjec-ted -to gas chromatog.raphy and ~ound to contain 19.2 % (615 g = 4.52 mol) of methan0phosphonous acid isobu-tyles-ter ~90.5 % of the theoretical).

EXAMPLE 4: (Diisobu-tylphosphite; cf. equation (1)) Column (2) was supplied with 900 ml o~ iso-butanol and 157 g/h (1.14 mol) of phosphorus trichloride and 386 g/h (5.22 mo.ls) o~ iso-bu*anol were added thereto, in the manner described in Example 1. Reaction product was removed continuously from the circulationevaporator (1) through line .(7), at a temperature of 135C in the . . .
column base portion. The temperature at -the head of the column dropped from 108C down to 84C. After 3 hours~ -the experiment was interrupted, the column base.
was freed completely from the material therein (altogether 874 g~ and the material was subjected to gas chromato-gr.aphy. The specimen tested contained 71.6 weight %
(626 g = 3.23 mols) o~ diisobutyl phosphite (94.4 % of the theoretical). The head distilla-te (receiver 5) contained 3.84 mols of hydrogen chloride and a ~urther 2..96 mols o~ hydrogen chloride was in the off-gas ~crùbber(6) placed downstream thereof. ~:

. ~
- EXAMPLE
-~ . . (Methanephosphonic acid diisobutylester; c~
equation (4)). . -~
Column (2) ~ras supplied with 900 ml of iso-bu-tano]., ..
~hich was heated to boilin~ ~therein and then admixed, in the manner described in Example 1, with 144 g/h (i.08 mols) .
.
. - - , . ~ :
. . -' -` ., 4;3 of me-thanephosphonic acid dichloride (in liquid preheated form) and with 304 g/h (4.10 mols) of iso-butanol. me reaction pro~uct was removed -through line (7) at a temperature of 132C in the column base portion. The temperature near the head of the column dropped from 108C down to ~1C. Altagether 4.24 mols of methane-phosphonic acid dichloride were introduced, the experiment was interrupted, the material in the column base portion was comple-tely removed therefrom (1083 g) and subjec-ted to gas chromatography. The specimen tested contained 72.7 weight % (787 g = 3.79 mols) of methanephosphonic '~~
acid dibutylester. The yield was 89.3 % of the theore--tical. The head product (receiver 5) contained 5.Z4 mols of hydrogen chloride and the off-gas scrubber (6) placed downstream thereof contained 2.~5 mols of hydrogen chloride.

EXAMPLE 6:
~Methanephosphonous acid ethylester; cf.equation (3)).
Column (2) was supplied, in the manner described in Example 1, with 900 ml (710 g - 15.4 mols) of ethanol which was admixed with 130 g/h ~1.11 mols) of methyldichloro-., . . ~ ,.
phosphine and 187 g/h (4.05 mols~ of ethanol. Altogether ; 2.11 mols of methyldichlorophosphine was introduced, the experiment was in-terrupted and the material in the~column base portion t401 g) was completely removed therefrom, once the temperature was at 83C. It was subjected to gas chromatography and found to co~tain 31.5 welght %
(126.3 g = 1.17 mols) of methanephosphonous acid mono-ethylester (55 ~ % of the theoretical).

, . . . .

Claims (3)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for making phosphorus-containing esters of the general formula:

, in which X stands for an alkyl group having from 1 to 3 carbon atoms, an aryl group or an alkoxy group having from 1 to 6 carbon atoms, Y stands for an alkoxy group having from 1 to 6 carbon atoms, and Z stands for a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms or an aryl group, by reacting phosphorus halides of the general formula:

in which A and B stand independently from one another, for a chlorine or bromine atom, an alkyl group having from 1 to 3 carbon atoms or an aryl group, C stands for a chlorine or bromine atom, and D stands for a free pair of electrons or an oxygen atom, with aliphatic alcohols having from 1 to 6 carbon atoms, which process comprises heating to boiling, in a reaction zone, the phosphorus halides and the aliphatic alcohol at temperatures within the range 60 to 150°C; passing the resulting hydrogen halide and alcohol in excess to the upper portion of the reaction zone, condensing it therein and removing it therefrom; and flowing resulting phosphorus-containing ester, if desired with an excess of aliphatic alcohol, to the lower portion of the reaction zone and removing it therefrom.
2. A process as claimed in claim 1, wherein the reaction is effected in the presence of nitrogen, argon or carbon dioxide as an inert gas.
3. A process as claimed in claim 1, wherein the reaction zone is supplied continuously, per mol of phosphorus halide, with 1.2 to 6 times the stoichiometric quantity of alcohol.
CA222,997A 1974-04-01 1975-03-25 Production of phosphorus-containing esters Expired CA1048043A (en)

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CA1048043A true CA1048043A (en) 1979-02-06

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BE (1) BE827308A (en)
CA (1) CA1048043A (en)
CH (1) CH611310A5 (en)
DD (1) DD119596A5 (en)
DE (1) DE2415757C2 (en)
DK (1) DK135275A (en)
FR (1) FR2306210A1 (en)
GB (1) GB1461376A (en)
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NL (1) NL183517C (en)
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DE2519192C2 (en) * 1975-04-30 1983-08-04 Hoechst Ag, 6230 Frankfurt Process for the production of phosphorus-containing esters
DE3245365A1 (en) * 1982-12-08 1984-06-14 Hoechst Ag, 6230 Frankfurt METHOD FOR PRODUCING ALKANPHOSPHONIC ACID ESTERS
MX2018003962A (en) 2015-09-29 2018-06-08 Bayer Cropscience Ag Method for producing phosphinates.

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FR455014A (en) * 1912-10-08 1913-07-21 Alexander Blair Thaw Improvements to stabilizers for airplanes

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FR2306210B1 (en) 1978-09-22
JPS5839157B2 (en) 1983-08-27
JPS50137930A (en) 1975-11-01
FR2306210A1 (en) 1976-10-29
SE7503559L (en) 1975-10-02
DD119596A5 (en) 1976-05-05
CH611310A5 (en) 1979-05-31
GB1461376A (en) 1977-01-13
BE827308A (en) 1975-09-29
SU633485A3 (en) 1978-11-15
SE414500B (en) 1980-08-04
IT1032478B (en) 1979-05-30
AT334913B (en) 1977-02-10
DK135275A (en) 1975-10-02
DE2415757C2 (en) 1982-10-14
NL183517C (en) 1988-11-16
NL183517B (en) 1988-06-16
ATA244075A (en) 1976-06-15
NL7503644A (en) 1975-10-03
DE2415757A1 (en) 1975-10-16

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